Alkyl chlorides are common functional groups in synthetic organic chemistry. However, the engagement of unactivated alkyl chlorides, especially tertiary alkyl chlorides, in transition-metal-catalyzed C-C bond formation remains challenging. Herein, we describe the development of a Ti-III-catalyzed radical addition of 2 degrees and 3 degrees alkyl chlorides to electron-deficient alkenes. Mechanistic data are consistent with inner-sphere activation of the C-Cl bond featuring Ti-III-mediated Cl atom abstraction. Evidence suggests that the active Ti-III catalyst is generated from the Ti-IV precursor in a Lewis-acid-assisted electron transfer process.